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Additives to enhance phosphorus compound removal in refinery desalting processes

a technology of phosphorus compound and additives, which is applied in the direction of water treatment, separation process, and other chemical processes, can solve the problems of rag layer inside the desalter vessel growing to such an extent, oil and water emulsions that are difficult to resolve, and complicated desalting process of particulate solids

Active Publication Date: 2005-11-03
BAKER HUGHES INC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The present invention provides a composition and method for transferring reactive phosphorus species from a hydrocarbon to an aqueous phase in a desalter operation. The composition includes a water-soluble hydroxyacid or a mixture of a water-soluble hydroxyacid and a mineral acid. The composition can be used to break emulsions of hydrocarbon and water without causing oil undercarry into the aqueous phase. The treated hydrocarbon emulsion includes a hydrocarbon phase, a water phase, and a composition for transferring reactive phosphorus species from the hydrocarbon phase to the water phase. The technical effect of the invention is to provide an effective way to remove reactive phosphorus species from crude oil during refining processes.

Problems solved by technology

Crude oil that contains a high percent of particulate solids can complicate the desalting process.
However, much of the solids in a crude oil from a field exists in tight water-in-oil emulsions.
That is, oil-wetted solids in high concentration in the crude may help form tight oil and water emulsions that are difficult to resolve.
The rag layer inside the desalter vessel may grow to such an extent that some of it will be inadvertently discharged with the water phase.
This is a problem for the waste water treatment plant since the rag layer still contains a high percentage of unresolved emulsified oil.
In addition to complicating the desalter operation, phosphorus and other contaminants are of particular concern to further downstream processing.
Additionally, many refineries in Canada and the northern US have experienced fouling of tower trays with deposits that have been analyzed to contain phosphorus.
Nonyl phenol resins have been used as desalting additives in the past, but these materials have come under suspicion as possible hormonal mimics and are ineffective by themselves of removing metals such as calcium or iron.

Method used

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  • Additives to enhance phosphorus compound removal in refinery desalting processes
  • Additives to enhance phosphorus compound removal in refinery desalting processes
  • Additives to enhance phosphorus compound removal in refinery desalting processes

Examples

Experimental program
Comparison scheme
Effect test

examples 84-110

[0086] Examples 84-110 were conducted using the same EDDA Test Method and analytical method described above. All of the tests were conducted on the same sample of crude oil. This sample of western Canadian crude oil was from a refinery experiencing severing fouling with phosphorus-based deposits. The EDDA tests were run at 100° C. for all of the tests and 5.5% wash water was used in each test. After the crude oil was treated and processed in the EDDA, the effluent water was collected and sent for analysis to determine the ion content in solution by ICP. The oil samples were ashed using microwave digestion and the resulting aqueous solution was analyzed by ICP. The various compositions tested are given in Table VII.

TABLE VIIAdditiveCompositionAdditive G98% glycolic acid (70%) 2% Magna 240 corrosion inhibitoravailable from Baker PetroliteAdditive H95% gluconic acid 5% citric acidAdditive J95% glycolic acid 4% thioglycolic acidBlend XBlend of non-ionic emulsion breakersavailable from...

examples 84-93

[0087] In these Examples, all samples were processed in the EDDA to simulate a desalting process. The first sample, Example 84, had no emulsion breaker of acid added, but was desalted. The rest of the samples except the wash water (Example 93) were treated with metals removal chemistry in addition to an emulsion breaker to help resolve the emulsion. In this study, Additive G at 20 ppm (Example 85) and in the other Examples 86, 89 and 90 effectively removed Ca and Fe from the crude oil. The treatment also reduced P content by about 25%.

TABLE VIIIEx.Sample Identification84Raw crude (Blank sample)85Treat at 20 ppm of Additive G, Desalter crude86Treat at 30 ppm of Additive G, Desalter crude87Treat at 30 ppm of Additive H, Desalter crude88Treat at 30 ppm of Additive J, Desalter crude89Treat at 20 ppm of Additive G, Effluent water90Treat at 30 ppm of Additive G, Effluent water91Treat at 30 ppm of Additive H, Effluent water92Treat at 30 ppm of Additive J, Effluent water93Wash water

[0088]...

example 94-95

[0089] In these Examples it may be seen that only 10 ppm of Additive G was required to remove most of the Ca and Fe. Again, the P seems to be reduced by about 25%.

TABLE XEx.Sample Identification94Treat with Blend X @ 10 ppm-vAdditive G @ 100 ppm-vWash water rate 5.5%Mix ΔP = 12 psigEffluent water95Treat with Blend Y @ 10 ppm-vAdditive G @ 100 ppm-vWash water rate 5.5%Mix ΔP = 12 psigDesalter crude

[0090]

TABLE XIICP EDDA Test Results (ppm - wt / wt), Examples 94-95Ex.NaKMgCaMoFeCuZnAl94146060.669.143376.32.88.71.8950.41.21.42.00.8Ex.BaBeCdCrPbMnNiB940.20.40.90.32.0950.53.11.3Ex.SrSiPSTiVSn949.34.24.8365952.83.0NR6.50.5

NR = Not run

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Abstract

Reactive phosphorus species can be removed or transferred from a hydrocarbon phase to a water phase in an emulsion breaking process by using a composition that contains water-soluble hydroxyacids. Suitable water-soluble hydroxy-acids include, but are not necessarily limited to glycolic acid, gluconic acid, C2-C4 alpha-hydroxy acids, poly-hydroxy carboxylic acids, thioglycolic acid, chloroacetic acid, polymeric forms of the above hydroxyacids, poly-glycolic esters, glycolate ethers, and ammonium salt and alkali metal salts of these hydroxyacids, and mixtures thereof. The composition may optionally include a mineral acid to reduce the pH of the desalter wash water. A solvent may be optionally included in the composition. The invention permits transfer of reactive phosphorus species into the aqueous phase with little or no hydrocarbon phase undercarry into the aqueous phase. The composition is particularly useful in treating crude oil emulsions, and in removing calcium and other metals therefrom.

Description

CROSS-REFERENCE TO RELATED APPLICATION [0001] This application is a continuation-in-part application from U.S. patent application Ser. No. 10 / 649,921 filed Aug. 27, 2003 that claims the benefit of U.S. Provisional Application No. 60 / 407,139 filed Aug. 30, 2002.FIELD OF THE INVENTION [0002] The present invention relates to methods and compositions for separating emulsions of hydrocarbons and water, and more particularly relates, in one embodiment, to methods and compositions for transferring reactive phosphorus species to an aqueous phase in an emulsion breaking process. BACKGROUND OF THE INVENTION [0003] In an oil refinery, the desalting of crude oil has been practiced for many years. The crude is usually contaminated from several sources, including, but not necessarily limited to: [0004] Brine contamination in the crude oil as a result of the brine associated with the oil in the ground; [0005] Minerals, clay, silt, and sand from the formation around the oil well bore; [0006] Metals...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): B01D17/05B01D17/02C10G17/04C10G31/08C10G33/02C10G33/04
CPCB01D17/0217C10G17/04C10G31/08C10G33/02C10G33/04B01D17/047C10G2300/202C10G2300/205C10G2300/44C10G2300/80C10G2300/805C10L2290/545
Inventor KREMER, LAWRENCE N.NGUYEN, TRAN M.WEERS, JERRY J.
Owner BAKER HUGHES INC
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